We demonstrate the production of nonwoven mats of high-temperature organic and inorganic fibers by electrospinning. Specifically, glass/ceramic (tetraethylorthosilicate-SiO) and fire-blanket (polydiphenoxyphosphazene-PDPP) precursors are electrospun, and the resulting fibers are characterized by scanning electron microscopy, thermogravimetric analysis, and infrared (IR) spectroscopy. We find that the SiO fibers are smaller in diameter and more uniform than the PDPP fibers, and stable to higher temperatures. We also coat these fiber systems with several rare-earth nitrates, and find that these coatings can be used to selectively modify the near-IR spectra of the fibers. This work extends the use of electrospinning into two new classes of materials, and demonstrates that we can subsequently modify the optical properties of the electrospun fibers. (C) 2003 American Vacuum Society.